Hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units

ABSTRACT

A hydroprocessing co-catalyst composition may comprise in an embodiment a first component comprising co-catalyst particles and a liquid carrier, and a second component comprising a dispersant and a dispersant diluent. The co-catalyst particles may be in the micron size range, and the dispersant may promote dispersion of the co-catalyst particles in materials such as the liquid carrier, the dispersant diluent, and combinations thereof. Methods of introducing a hydroprocessing co-catalyst composition into a hydroprocessing system are also disclosed.

TECHNICAL FIELD

The present invention relates to hydroprocessing co-catalystcompositions and methods of introduction thereof into hydroprocessingunits.

BACKGROUND

Heavy feedstocks, such as vacuum gas oils and residuum, containrelatively high concentrations of S-, N-, O-, and polynuclear aromaticcontaining compounds, as well as complex Ni- and V-containing compoundsand asphaltenes. As a result, heavy oil is particularly difficult toupgrade in refinery operations. Metals contained in the oil tend torapidly deactivate catalysts with which they come in contact during theupgrading process. In addition, sulfur and nitrogen are difficult toremove to the extent necessary for further processing of the upgradedproducts from heavy oil processing.

Furthermore, heavy oil components thermally crack during processing toform free radicals, which quickly combine to make sediment and cokeprecursors unless suppressed by active catalysis. During conventionalhydroprocessing of heavy oils, high molecular weight coke precursors andcontaminants that are deposited on catalysts quickly reduce catalyticactivity.

One type of conventional heavy oil processing uses an ebullated bedsystem, in which the catalyst is maintained in a fluidized state withinthe reaction zone. At periodic intervals, a portion of the fluidized bedof catalyst, along with a small portion of fluidizing liquid, is removedfrom the system. A comparable amount of catalyst is added to the systemto maintain a constant quantity of catalyst in the system at any onetime.

In conventional heavy oil upgrading, e.g., using an ebullated bed systemthat relies solely on a conventional pelletized hydroprocessingcatalyst, poorly converted or unconverted feed may precipitate assediment or sludge. Sediment can then plug equipment leading to shorterruntime and/or operational issues, as well as poor product quality. Theformation of sediment or sludge typically increases with conversion andfeed difficulty. For this reason, the conversion or ability to process aflexible array of feeds is limited in these units.

Thus, there is a need for improved hydroprocessing catalyst systems thatare more efficient, permit an increase in conversion and/or the use of awider range of feedstocks in a cost-effective manner, as compared withthe prior art. There is a further need for methods of introducing aco-catalyst into a hydroprocessing unit.

SUMMARY

One embodiment of the invention is a hydroprocessing co-catalystcomposition comprising a liquid carrier comprising oil and co-catalystparticles in admixture with the liquid carrier, wherein the co-catalystparticles are hydrophilic and have a mean particle size between about 2microns and 100 microns.

Another embodiment of the invention is a hydroprocessing co-catalystcomposition comprising co-catalyst particles having a mean particle sizebetween about 2 microns and 100 microns, and a liquid carrier inadmixture with the co-catalyst particles, wherein the compositioncomprises from about 5 wt. % to 50 wt. % of the co-catalyst particles,and the liquid carrier comprises oil.

A further embodiment of the invention is a hydroprocessing co-catalystcomposition comprising a liquid carrier comprising oil having a boilingrange from about 350° F. to 1125° F., and co-catalyst particles having amean particle size between about 4 microns and 40 microns; wherein thecomposition comprises from about 5 wt. % to 50 wt. % of the co-catalystparticles and the co-catalyst particles comprise a support comprising amaterial selected from alumina, aluminosilicates, silica, boria,magnesia, titania, and combinations thereof.

In yet another embodiment, the invention is a hydroprocessingco-catalyst comprising a composition A comprising a liquid carrier andco-catalyst particles having a mean particle size between about 2microns and 100 microns, and a composition B comprising a dispersant anda dispersant diluent.

In still a further embodiment, the invention is a hydroprocessingco-catalyst comprising a liquid carrier, co-catalyst particles having amean particle size between about 2 microns and 100 microns, adispersant, and a dispersant diluent, wherein the hydroprocessingco-catalyst comprises from about 3 wt. % to 50 wt. % of the co-catalystparticles.

In yet a further embodiment, the invention is a hydroprocessingco-catalyst prepared by a method comprising the steps of providing acomposition A comprising co-catalyst particles and a liquid carrier,providing a composition B comprising a dispersant and a dispersantdiluent, and combining composition A with composition B to provide asuspension of the co-catalyst particles.

In another embodiment, the invention comprises a method of introducingco-catalyst particles into a hydroprocessing system, the methodcomprising providing a composition A comprising the co-catalystparticles and a liquid carrier; providing a composition B comprising adispersant and a dispersant diluent; combining composition B withcomposition A to form a composition C, wherein composition C comprises asuspension of the co-catalyst particles; and after the combining step,contacting the co-catalyst particles with a hydrocarbon feed of thehydroprocessing system.

In a further embodiment the invention is a method of introducingco-catalyst particles into a hydroprocessing system, the methodcomprising providing a composition A comprising the co-catalystparticles and a liquid carrier, wherein the co-catalyst particles have amean particle size between about 2 microns and 100 microns, and theliquid carrier comprises oil; providing a composition B comprising adispersant and a dispersant diluent; combining composition A withcomposition B to form a composition C; and contacting composition C witha hydrocarbon feed of the hydroprocessing system.

In yet another embodiment the invention is a method of introducingco-catalyst particles into a hydroprocessing system, the methodcomprising providing a composition A comprising the co-catalystparticles and a liquid carrier; providing a composition B comprising adispersant and a dispersant diluent; combining composition B withcomposition A to form a composition C, wherein composition C comprises asuspension of the co-catalyst particles; and contacting composition Cwith a hydrocarbon feed of the hydroprocessing system such that theco-catalyst particles are entrained with the hydrocarbon feed within thehydroprocessing system. The co-catalyst particles may comprise a supportcomprising a material selected from alumina, aluminosilicates, silica,boria, magnesia, titania, and combinations thereof, and the co-catalystparticles may have a mean particle size between about 2 microns and 100microns.

As used herein, the terms “comprising” and “comprises” mean theinclusion of named elements or steps that are identified following thoseterms, but not necessarily excluding other unnamed elements or steps.

DETAILED DESCRIPTION

The upgrading of residuum and other heavy feedstocks in hydroprocessingunits is an important process in petroleum refining for producing highervalue products. One type of heavy oil hydroprocessing unit uses anebullated bed system, in which the catalyst is maintained in a fluidizedstate within the reaction zone.

An ebullated bed heavy oil processing system that employs a dualcatalyst system for heavy oil hydroprocessing is disclosed, for example,in commonly assigned co-pending U.S. patent application Ser. No.13/331,479, Hydroprocessing catalysts and methods for making thereoffiled Dec. 20, 2011, the disclosure of which is incorporated byreference herein in its entirety.

Disclosed herein are new co-catalyst compositions, which greatly augmentthe catalytic activity of conventional pellet hydroprocessing catalyststo enhance the performance of hydroprocessing units, such as LC-Finingand H-Oil ebullated bed units, for processing heavy oil feedstocks. Incontrast to the prior art, micron-sized solid particles of co-catalystmay be suspended in, and move with, the residuum feed stream, such thatthe co-catalyst particles may percolate not only through the ebullatedbed reaction zone, but also throughout the hydroprocessing unit. Becauseparticles of the co-catalyst disclosed herein can migrate with the feedstream through the hydroprocessing unit, the co-catalyst providessubstantial additional catalytic activity to enhance residuumconversion, while minimizing the formation of undesirable sediment orsludge.

In addition, the co-catalyst particles provide additional surface areaand pore volume to adsorb contaminants from the residuum feed, resultingin reduced aging of the ebullated bed portion of the hydroprocessingcatalyst system and a much longer runtime for the hydroprocessing unit.

Accordingly, the addition of the co-catalyst to an ebullated bedhydroprocessing unit allows for improved operation, including increasedheavy oil feedstock conversion, and/or the ability to process moredifficult (e.g., heavier and/or more contaminated) feeds.

In an embodiment, the performance of the co-catalyst, e.g., in anebullated bed hydroprocessing unit, may be increased by achieving gooddispersion of the micron-sized solid co-catalyst particles into thehydrocarbon feed (e.g., residuum). Such dispersion of the co-catalystparticles in the feed may be enabled not only by various chemical andphysical attributes of the co-catalyst composition, but also by novelmethods and approaches, as disclosed herein, for introducing theco-catalyst into the hydroprocessing unit.

In an embodiment, the co-catalyst composition may be miscible with acatalyst introduction diluent comprising a hydrocarbonaceous oil, andthe catalyst introduction diluent may be combined with the co-catalystcomposition before introducing the diluent/co-catalyst mixture into theresiduum feed. In another embodiment, the co-catalyst composition may bemiscible with the residuum feed itself. In an embodiment, compositionsas disclosed herein may be safely and conveniently handled andtransported.

Therefore, the co-catalyst compositions as provided herein provide manyadvantages for heavy oil hydroprocessing as compared with the prior art,including the major economic advantage of enhancing the conversionand/or allowing for more difficult feedstocks to be processed withoutthe typical increase in sediment or sludge make associated with suchmore severe operation.

As used herein, “heavy oil” feed or feedstock refers to heavy andultra-heavy crudes, including but not limited to resids, coals, bitumen,tar sands, oils obtained from the thermo-decomposition of wasteproducts, polymers, biomasses, oils deriving from coke and oil shales,and the like. Heavy oil feedstock may be liquid, semi-solid, and/orsolid. Examples of heavy oil feedstock include but are not limited toCanada Tar sands, vacuum resid from Brazilian Santos and Campos basins,Egyptian Gulf of Suez, Chad, Venezuelan Zulia, Malaysia, and IndonesiaSumatra. Other examples of heavy oil feedstock include residuum leftover from refinery processes, including “bottom of the barrel” and“residuum” (or “resid”), atmospheric tower bottoms, which have a boilingpoint of at least 650° F. (343° C.), or vacuum tower bottoms, which havea boiling point of at least 975° F. (524° C.), or “resid pitch” and“vacuum residue” which have a boiling point of 975° F. (524° C.) orgreater.

Co-Catalyst Compositions for Hydroprocessing

In an embodiment, a hydroprocessing co-catalyst composition may comprisea first component comprising co-catalyst particles and a secondcomponent comprising a dispersant. Herein, the first component may bereferred to as Composition A, and the second component may be referredto as Composition B.

i) Composition A

In an embodiment we provide a Composition A, which may comprise a liquidcarrier and co-catalyst particles. The co-catalyst particles may be inadmixture with the liquid carrier. In an embodiment, the liquid carriermay comprise oil. Such oil may comprise, for example, petroleum derivedoil. In an embodiment, oil comprising the liquid carrier may have aboiling range from about 350° F. to 1125° F., or from about 550° F. to1100° F., or from about 550° F. to 950° F. As a non-limiting example,the liquid carrier may comprise a material selected from vacuum gas oil,light vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavydiesel, and combinations thereof.

In an embodiment, the co-catalyst particles may be hydrophilic. Theco-catalyst particles may comprise a support. The support may comprise amaterial selected from alumina, aluminosilicates, silica, as well asother refractory inorganic oxides, including boria, magnesia, titania,and the like and combinations thereof. The co-catalyst support of thepresent invention can be manufactured by any conventional techniques. Inan embodiment, the co-catalyst particles may further comprise one ormore metal components. In an embodiment, the support or base may containcatalytic metals, in particular metals from Group VIB of the PeriodicTable, including molybdenum and/or tungsten, and/or from Group VIII ofthe Periodic Table, in particular nickel and/or cobalt. Catalytic metalsmay be placed onto the support by conventional techniques, includingcomulling, impregnation, and the like.

In an embodiment, the co-catalyst particles may be synthesized, groundor milled to achieve co-catalyst particles having a particle size in therange from about 1 micron (μm) to 100 microns, or from about 2 micronsto 60 microns, or from about 2 microns to 30 microns. In anotherembodiment, the co-catalyst particles may have a mean particle sizebetween about 2 microns and 100 microns, or between about 4 microns and40 microns, or between about 4 microns and 30 microns.

In an embodiment, the co-catalyst particles may be suspended in theliquid carrier. In an embodiment, the co-catalyst particles may besuspensible in the liquid carrier in the absence of an extrinsicdispersant. In an embodiment, a liquid carrier may itself contain one ormore intrinsic dispersive agents that promote dispersion of theco-catalyst particles in the liquid carrier, such that the liquidcarrier is inherently capable of suspending the co-catalyst particlestherein without the addition of an extrinsic dispersant to the liquidcarrier or to the co-catalyst particles.

In an embodiment, Composition A may comprise from about 5 wt. % to 50wt. % of the co-catalyst particles, in another embodiment from about 10wt. % to 40 wt. %, or in a further embodiment from about 15 wt. % to 30wt. %. In an embodiment, Composition A may comprise from about 50 wt. %to 95 wt. % of the liquid carrier, or from about 60 wt. % to 90 wt. %,or from about 70 wt. % to 85 wt. %.

In an embodiment, the co-catalyst particles may be synthesized orprepared, e.g., by grinding, milling, and the like, using techniques andequipment known in the art, including but not limited to: hammer mill,roller mill, ball mill, jet mill, attrition mill, grinding mill, mediaagitation mill, and the like, or utilizing synthesis techniques known inthe art, including precipitation, atomization, gelling and the like. Theco-catalyst particles may be sorted to provide suitable sizedistributions, e.g., according to a particular requirement orapplication of a co-catalyst composition.

In an embodiment, Composition A may have a viscosity, at about 70° F.,in the range from about 1000 centipoise to 5000 centipoise, in anotherembodiment from about 1500 centipoise to 4000 centipoise, or in afurther embodiment from about 2000 centipoise to 3500 centipoise.

ii) Composition B

In an embodiment, Composition B may comprise a dispersant and adispersant diluent. In an embodiment, the dispersant may be in admixturewith the dispersant diluent. As an example, the dispersant may compriseone or more components that are capable of promoting dispersion ofco-catalyst particles in a lipophilic liquid. Such component(s) maycomprise, for example, surface active materials, such as non-ionic,anionic, cationic, or amphoteric surfactants.

In an embodiment, the dispersant may be added to the dispersant diluentin an amount such that Composition B may comprise from about 10 wt. % to95 wt. % of the dispersant, or from about 20 wt. % to 80 wt. %, or fromabout 30 wt. % to 70 wt. %. In one embodiment, the dispersant may be inthe liquid state over a broad temperature range, for example, from about65° F. to 500° F., or from about 70° F. to 350° F.

In an embodiment, the dispersant may comprise a plurality of components.In an embodiment, the dispersant may comprise polyisobutylenesuccinimide. In an embodiment, the dispersant may further comprise amaterial selected from carboxylic acids, dicarboxylic acids, andcombinations thereof. In one embodiment, the dispersant may comprisepolyisobutylene succinimide and a carboxylic acid such as oleic acid. Ina sub-embodiment, Composition B may comprise from about 10 wt. % to 30wt. % of polyisobutylene succinimide and from about 30 wt. % to 65 wt. %of oleic acid.

In an embodiment, the dispersant diluent may comprise oil. In anembodiment, oil comprising the dispersant diluent may have a boilingrange from about 350° F. to 1125° F., or from about 550° F. to 1100° F.,or from about 550° F. to 950° F. As a non-limiting example, thedispersant diluent may comprise a material selected from vacuum gas oil,light vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavydiesel, and combinations thereof.

iii) Composition C

In another embodiment we provide a Composition C, which may comprise ahydroprocessing co-catalyst composition for introduction orincorporation into a hydroprocessing system. In an embodiment.Composition C may be used, for example, as an adjunct to a conventionalcatalyst in a hydroprocessing (e.g., ebullated bed) system forhydroprocessing a heavy hydrocarbon feed.

Composition C may comprise Composition A (supra) and Composition B(supra). In an embodiment, Composition A and Composition B may beprovided in separate containers or vessels. As an example, Composition Amay be provided, or contained, in a first vessel, and Composition B maybe provided, or contained, in a second vessel. In another embodiment,Composition C may comprise Composition A in admixture with CompositionB.

Composition A may comprise a liquid carrier and co-catalyst particles,as described hereinabove. Composition B may comprise a dispersant and adispersant diluent, also as described hereinabove. Composition C may beprepared by combining Composition A with Composition B. In anembodiment, Composition A and Composition B may be combined at aComposition A/Composition B volume ratio in the range from about 1:20 to60:1, or from about 1:10 to 50:1, or from about 1:5 to 45:1, to provideComposition C. In an embodiment, the liquid carrier of Composition A maybe miscible with the dispersant diluent of Composition B to form asingle phase homogeneous liquid.

In another embodiment, Composition C may be prepared by separatelycombining one or more dispersant components with Composition A. As anexample, one or more materials selected from polyisobutylenesuccinimide, carboxylic acids, and dicarboxylic acids, may be addedseparately to Composition A.

Composition C may comprise a suspension of the co-catalyst particlesdispersed in a mixture of the liquid carrier and the dispersant diluent.In an embodiment, Composition C may comprise a slurry. Composition C mayhave a viscosity, at a temperature of about 70° F. in the range fromabout 100 centipoise to 3000 centipoise, or from about 150 centipoise to2000 centipoise, or from about 200 centipoise to 1000 centipoise. In anembodiment, each of the liquid carrier and the dispersant diluent maycomprise oil.

In an embodiment, the co-catalyst particles may comprise a support. Thesupport may comprise a material selected from alumina, aluminosilicates,silica, as well as other refractory inorganic oxides, including boria,magnesia, titania, and the like, and combinations thereof. Theco-catalyst support of the present invention can be manufactured by anyconventional techniques. In an embodiment, the co-catalyst particles mayfurther comprise one or more active metal components. In an embodiment,the support or base may contain catalytic metals, in particular metalsfrom Group VIB of the Periodic Table, including molybdenum and/ortungsten, and/or from Group III of the periodic Table, in particularnickel and/or cobalt. Catalytic metals may be placed onto the support byconventional techniques, including comulling, impregnation, and thelike.

In an embodiment, the co-catalyst particles may have a particle size inthe range from about 1 micron (μm) to 100 microns, or from about 2microns to 60 microns, or from about 2 microns to 30 microns. In anotherembodiment, the co-catalyst particles may have a mean particle sizebetween about 2 microns and 100 microns, or between about 4 microns and40 microns, or between about 4 microns and 30 microns. In an embodiment,Composition C may comprise from about 3 wt. % to 50 wt. % of theco-catalyst particles, or from about 5 wt. % to 40 wt. %, or from about10 wt. % to 30 wt. %.

The dispersant may comprise polyisobutylene succinimide. In anembodiment, the dispersant may comprise a plurality of components. In anembodiment, the dispersant may comprise a material selected fromcarboxylic acids, dicarboxylic acids, and combinations thereof. In asub-embodiment, the dispersant may comprise polyisobutylene succinimideand oleic acid.

In an embodiment, the dispersant diluent may comprise oil. In anembodiment, oil comprising the dispersant diluent may have a boilingrange from about 350° F. to 1125° F., or from about 550° F. to 1100° F.,or from about 550° F. to 950° F. As a non-limiting example, thedispersant diluent may comprise a material selected from vacuum gas oil,light vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavydiesel, and combinations thereof.

In an embodiment, the dispersant diluent may be miscible with the liquidcarrier to form a single phase homogeneous liquid. In an embodiment, thedispersant diluent may comprise a first oil, and the liquid carrier maycomprise a second oil. The first oil and the second oil may be the sameor different. In another embodiment, each of the first oil and thesecond oil may comprise vacuum gas oil or lube oil base stock.

In another embodiment, Composition C may comprise co-catalyst particles,a liquid carrier, a dispersant, and a dispersant diluent. The liquidcarrier may be miscible with the dispersant diluent to form a singlephase homogeneous liquid, and Composition C may comprise a suspension ofthe co-catalyst particles dispersed in the homogeneous liquid. In anembodiment, each of the liquid carrier and the dispersant diluent maycomprise oil.

In an embodiment, Composition C may comprise from about 3 wt. % to 50wt. % of the co-catalyst particles, or from about 5 wt. % to 40 wt. %,or from about 10 wt. % to 30 wt. %. In an embodiment, the co-catalystparticles may have a particle size in the range from about 1 micron (μm)to 100 microns, or from about 2 microns to 60 microns, or from about 2microns to 30 microns. In another embodiment, the co-catalyst particlesmay have a mean particle size between about 2 microns and 100 microns,or between about 4 microns and 40 microns, or between about 4 micronsand 30 microns.

In an embodiment, the co-catalyst particles may comprise a support. Thesupport may comprise a material selected from alumina, aluminosilicates,silica, as well as other refractory inorganic oxides, including boria,magnesia, titania, and the like and combinations thereof. Theco-catalyst support of the present invention can be manufactured by anyconventional techniques.

In another embodiment a hydroprocessing co-catalyst composition, such asComposition C, may be prepared by a method comprising the steps of: i)providing a Composition A comprising co-catalyst particles and a liquidcarrier, ii) providing a Composition B comprising a dispersant and adispersant diluent; and iii) combining Composition A with Composition Bto provide a suspension of the co-catalyst particles. In an embodiment,step i) may comprise combining the co-catalyst particles with the liquidcarrier to provide a suspension of the co-catalyst in the liquidcarrier.

In an embodiment, Composition C may comprise from about 3 wt. % to 50wt. % of the co-catalyst particles, or from about 5 wt. % to 40 wt. %,or from about 10 wt. % to 30 wt. %. In an embodiment, Composition C maycomprise from about 50 wt. % to 90 wt. % of the liquid carrier, or fromabout 60 wt. % to 85 wt. %, or from about 65 wt. % to 80 wt. %.

In an embodiment, the co-catalyst particles may have a particle size inthe range from about 1 micron (μm) to 100 microns, or from about 2microns to 60 microns, or from about 2 microns to 30 microns. In anotherembodiment, the co-catalyst particles may have a mean particle sizebetween about 2 microns and 100 microns, or between about 4 microns and40 microns, or between about 4 microns and 30 microns.

In an embodiment, the co-catalyst particles may be hydrophilic. In anembodiment, the co-catalyst particles may comprise a support. Thesupport may comprise a material selected from alumina, aluminosilicates,silica, as well as other refractory inorganic oxides, including boria,magnesia, titania, and the like and combinations thereof. Theco-catalyst support of the present invention can be manufactured by anyconventional techniques. In an embodiment, the co-catalyst particles mayfurther comprise one or more active metal components. In an embodiment,the support or base may contain catalytic metals, in particular metalsfrom Group VIB of the Periodic Table, including molybdenum and/ortungsten, and/or from Group III of the periodic Table, in particularnickel and/or cobalt. Catalytic metals may be placed onto the support byconventional techniques, including comulling, impregnation and the like.

In an embodiment, the dispersant provided in Composition B may compriseone or more components for promoting the dispersion of the co-catalystparticles. In an embodiment, the dispersant may comprise, for example, asurface active material, such as a non-ionic, anionic, cationic, oramphoteric surfactant. In an embodiment, the dispersant may be added tothe dispersant diluent in an amount such that Composition C may comprisefrom about 2 wt. % to 60 wt. % of the dispersant, or from about 4 wt. %to 40 wt. %, or from about 5 wt. % to 20 wt. %. In one embodiment, thedispersant may be in the liquid state over a broad temperature range,for example, from about 65° F. to 500° F., or from about 70° F. to 350°F.

In an embodiment, the dispersant may comprise a plurality of components.In an embodiment, the dispersant may comprise polyisobutylenesuccinimide. In an embodiment, the dispersant may further comprise amaterial selected from carboxylic acids, dicarboxylic acids, andcombinations thereof. In one embodiment, the dispersant may comprisepolyisobutylene succinimide and a carboxylic acid such as oleic acid. Inan embodiment, Composition C may comprise from about 0.5 wt. % to 10.0wt. % of polyisobutylene succinimide, or from about 1.0 wt. % to 7.5 wt.%, or from about 1.5 wt. % to 5.0 wt. % of polyisobutylene succinimide.In an embodiment, Composition C may further comprise from about 1.0 wt.% to 15.0 wt. % of oleic acid, or from about 2.0 wt. % to 10.0 wt. %, orfrom about 3.0 wt. % to 7.5 wt. % of oleic acid.

In an embodiment, the dispersant diluent may comprise oil. In anembodiment, oil comprising the dispersant diluent may have a boilingrange from about 350° F. to 1125° F., or from about 550° F. to 1100° F.,or from about 550° F. to 950° F. As a non-limiting example, thedispersant diluent may comprise a material selected from vacuum gas oil,light vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavydiesel, and combinations thereof.

In an embodiment, the liquid carrier may be miscible with the dispersantdiluent to form a single phase homogeneous liquid, and Composition C maycomprise a suspension of the co-catalyst particles dispersed in thehomogeneous liquid. In an embodiment, the dispersant may promotedispersion of the co-catalyst particles in the homogeneous liquid. Thedispersant may prevent or delay aggregation or flocculation of theco-catalyst particles in Composition C, and may prevent or delaysedimentation or settling of the co-catalyst particles. In anembodiment, the dispersant may also promote dispersion of theco-catalyst particles in a refinery stream or a hydrocarbon feed to ahydroprocessing unit.

While not being bound by any theory, in an embodiment a plurality ofdispersant molecules may be adsorbed by, or otherwise associated with,each of the co-catalyst particles. In an embodiment, the dispersantmolecules may each have an elongated or sterically bulky portionextending from the co-catalyst particles, thereby preventing directcontact between adjacent co-catalyst particles such that flocculation ofthe suspended co-catalyst particles does not occur.

In one embodiment, Composition C may comprise a slurry. In anembodiment, Composition C may have a viscosity, at about 70° F., in therange from about 100 centipoise to 3000 centipoise, in anotherembodiment from about 150 centipoise to 2000 centipoise, or in a furtherembodiment from about 200 centipoise to 1000 centipoise. In anembodiment, the solids (particulate) content of Composition C may bevaried, for example, to optimize the catalytic activity thereof. Inanother embodiment, the viscosity of one or more of Compositions A, B,and C may be varied, for example, to facilitate production, transport,pumpability, and/or storage thereof.

In an embodiment, the viscosity of Composition C may be varied, forexample, by selecting a more or less viscous liquid carrier, byselecting a more or less viscous dispersant diluent, by varying thesolids content, or by a combination thereof. In an embodiment, thecomposition of Composition C may be adjusted to provide a co-catalystcomposition that not only has good catalytic activity, but that is alsoconvenient to transport, handle, and introduce into the hydroprocessingunit.

In an embodiment, Composition C may be injected into the hydroprocessingsystem directly. In another embodiment, Composition C may be combinedwith a catalyst introduction diluent to provide a Composition C/diluentmixture preparatory to the introduction of the co-catalyst particlesinto a hydroprocessing system. The Composition C/diluent mixture may bereferred to herein as Composition D. In an embodiment, the dispersantmay promote dispersion of the co-catalyst particles in the catalystintroduction diluent or Composition D. In another embodiment, thedispersant may promote dispersion of the co-catalyst particles in thehydrocarbon feed.

The catalyst introduction diluent may comprise, for example, petroleumderived oil. The catalyst introduction diluent may have a boiling rangefrom about 350° F. to 1125° F., or from about 450° F. to 1100° F., orfrom about 650° F. to 1000° F. In an embodiment, the catalystintroduction diluent may comprise, for example, a refinery stream or afeedstock for a refinery process. Exemplary catalyst introductiondiluents may include, without limitation, vacuum gas oil, light gas oil,diesel, light cycle oil, medium cycle oil, decant oil, flush oil, cutterstocks, and combinations thereof.

In an embodiment, Composition C may be miscible with the catalystintroduction diluent over a broad range of Composition C/diluentproportions to give a homogeneous liquid dispersion medium. In anembodiment, Composition C may be combined with the catalyst introductiondiluent at a diluent/Composition C volume ratio in the range from about1:1 to 200:1, or from about 2:1 to 100:1, or from about 3:1 to 50:1. Inan embodiment, Composition C may be miscible with the catalystintroduction diluent over a broad temperature range. For example,Composition C may be miscible with the catalyst introduction diluent ata temperature in the range from about 150° F. to 700° F., or from about200° F. to 500° F.

In an embodiment, the Composition C/diluent mixture may be contactedwith a hydrocarbon feed to a hydroprocessing system for the efficaciousdispersion of the co-catalyst composition into the hydrocarbon feed. Inan embodiment, the hydrocarbon feed may comprise, for example,atmospheric or vacuum residuum or other heavy oil feed to ahydroprocessing unit. In an embodiment, the co-catalyst particles ofComposition C may be sized for entrainment in the hydrocarbon streamthrough at least a portion of an ebullated bed hydroprocessing unit inone embodiment, or throughout the entire course of an ebullated bedhydroprocessing unit in another embodiment.

Methods for Making Co-Catalyst Compositions

In another embodiment we provide methods for making co-catalystcompositions. In an embodiment, a hydroprocessing co-catalystcomposition, such as Composition C, may be prepared by a methodcomprising the steps of providing a Composition A, which comprisesco-catalyst particles and a liquid carrier; and providing a CompositionB, which comprises a dispersant and a dispersant diluent.

The co-catalyst particles may be in admixture with the liquid carrier inComposition A. In an embodiment, the co-catalyst particles may becombined with the liquid carrier using one or more techniques known inthe art for mixing liquids with particulate solids. In an embodiment,Composition A may be prepared by combining the co-catalyst particleswith the liquid carrier so as to form a suspension of the co-catalystparticles. In an embodiment, the liquid carrier may comprise oil. Suchoil may comprise, for example, petroleum derived oil. In an embodiment,oil comprising the liquid carrier may have a boiling range from about350° F. to 1125° F., or from about 550° F. to 1100° F., or from about550° F. to 950° F. As a non-limiting example, the liquid carrier maycomprise a material selected from vacuum gas oil, light vacuum gas oil,heavy vacuum gas oil, lube oil base stock, heavy diesel, andcombinations thereof.

In an embodiment, the co-catalyst particles may be combined with theliquid carrier at a suitable temperature, which may be at, below, orabove ambient temperature. In embodiments wherein the liquid carrier maycomprise a viscous liquid, the co-catalyst particles may be combinedwith the liquid carrier at substantially above ambient temperature. Inan embodiment, the co-catalyst particles may be combined with the liquidcarrier at a temperature in the range from about 60° F. to 200° F., orfrom about 75° F. to 150° F.

In an embodiment, the co-catalyst particles may have a particle size inthe range from about 1 micron (μm) to 100 microns, or from about 2microns to 60 microns, or from about 2 microns to 30 microns. In anotherembodiment, the co-catalyst particles may have a mean particle sizebetween about 2 microns and 100 microns, or between about 4 microns and40 microns, or between about 4 microns and 30 microns.

In an embodiment, the co-catalyst particles may be hydrophilic. Theco-catalyst particles may comprise a support. The support may comprise amaterial selected from alumina, aluminosilicates, silica, as well asother refractory inorganic oxides, including boria, magnesia, titania,and the like, and combinations thereof. The co-catalyst support of thepresent invention can be manufactured by any conventional techniques. Inan embodiment, the co-catalyst particles may further comprise one ormore metal components. In an embodiment, the support or base may containcatalytic metals, in particular metals from Group VIB of the PeriodicTable, including molybdenum and/or tungsten, and/or from Group VIII ofthe Periodic Table, in particular nickel and/or cobalt. Catalytic metalsmay be placed onto the support by conventional techniques, includingcomulling, impregnation, and the like.

In an embodiment, Composition B may be prepared by combining thedispersant and the dispersant diluent such that the dispersant may be inadmixture with the dispersant diluent. In an embodiment, the dispersantmay comprise, for example, a surface active material, such as anon-ionic, anionic, cationic, or amphoteric surfactant.

The dispersant may serve to promote dispersion of the co-catalystparticles of Composition A upon combining Composition A with CompositionB. In an embodiment, the dispersant may be added to the dispersantdiluent in an amount such that Composition B may comprise from about 10wt. % to 95 wt. % of the dispersant, or from about 20 wt. % to 80 wt. %,or from about 30 wt. % to 70 wt. %. In one embodiment, the dispersantmay be in the liquid state over a broad temperature range, for example,from about 65° F. to 500° F., or from about 70° F. to 350° F.

In an embodiment, the dispersant may comprise a plurality of components.In an embodiment, the dispersant may comprise polyisobutylenesuccinimide. In an embodiment, the dispersant may comprise a materialselected from carboxylic acids, dicarboxylic acids, and combinationsthereof. In one embodiment, the dispersant may comprise polyisobutylenesuccinimide and a carboxylic acid such as oleic acid. In asub-embodiment. Composition B may comprise from about 10 wt. % to 30 wt.% of polyisobutylene succinimide and from about 30 wt. % to 65 wt. % ofoleic acid.

In an embodiment, oil comprising the dispersant diluent may have aboiling range from about 350° F. to 1125° F., or from about 550° F. to1100° F. or from about 550° F. to 950° F. As a non-limiting example, thedispersant diluent may comprise a material selected from vacuum gas oil,light vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavydiesel, and combinations thereof.

In an embodiment, Composition A and Composition B may be provided, e.g.,to a hydroprocessing unit or other refinery location, in separatevessels or containers. That is to say, in an embodiment, Composition Cmay be provided, e.g., to a hydroprocessing unit, as its componentparts, Composition A and Composition B. In another embodiment, a methodof making a hydroprocessing co-catalyst composition may further comprisecombining Composition A with Composition B to provide Composition C.

Composition C may comprise a suspension of the co-catalyst particlesdispersed in a mixture of the liquid carrier and the dispersant diluent.Such mixture may comprise a homogeneous liquid over a broad temperaturerange, e.g., from about 65° F. to 650° F., under hydroprocessingconditions (high pressure). In an embodiment, Composition A may becombined with Composition B at a Composition A/Composition B volumeratio in the range from about 1:20 to 60:1, or from about 1:10 to 50:1,or from about 1:5 to 45:1, to provide Composition C.

In an embodiment, the co-catalyst particles may be prepared, e.g., bygrinding, milling, and the like. The co-catalyst particles may be sortedto provide suitable size distributions for preparing a co-catalystcomposition having an appropriate level of catalytic activity, asuitable viscosity, and/or other characteristics for a particularhydroprocessing process or application. In an embodiment, theco-catalyst particles may be ground, pulverized, or crushed to thedesired particle size using techniques known in the art, e.g., via wetgrinding or dry grinding, and using equipment known in the art,including but not limited to: hammer mill, roller mill, ball mill, jetmill, attrition mill, grinding mill, media agitation mill, and the like.In an embodiment, the co-catalyst particles may be synthesized to thedesired size distributions utilizing forming techniques known in theart, including but not limited to precipitation, gelling, atomization,and the like.

In an embodiment, the co-catalyst particles may be synthesized, groundor milled to achieve co-catalyst particles having a particle size in therange from about 1 micron (μm) to 100 microns, or from about 2 micronsto 60 microns, or from about 2 microns to 30 microns. In anotherembodiment, the co-catalyst particles may have a mean particle sizebetween about 2 microns and 100 microns, or between about 4 microns and40 microns, or between about 4 microns and 30 microns.

In an embodiment, the dispersant may comprise a plurality of components.In an embodiment, the dispersant may comprise polyisobutylenesuccinimide. In an embodiment, the dispersant may further comprise amaterial selected from carboxylic acids, dicarboxylic acids, andcombinations thereof. In one embodiment, the dispersant may comprisepolyisobutylene succinimide and a carboxylic acid such as oleic acid. Ina sub-embodiment, Composition B may comprise from about 10 wt. % to 30wt. % of polyisobutylene succinimide and from about 30 wt. % to 65 wt. %of oleic acid.

In an embodiment, an amount of the dispersant to be used in preparingthe hydroprocessing co-catalyst composition (e.g., Composition C) may bevaried, for example, according to the total surface area of theco-catalyst particles. In one embodiment, the amount of dispersant inthe hydroprocessing co-catalyst composition may be proportional to theamount of co-catalyst particles in the hydroprocessing co-catalystcomposition. In an embodiment, Composition C may comprise from about 2wt. % to 60 wt. % of the dispersant, or from about 4 wt. % to 40 wt. %,or from about 5 wt. % to 20 wt. %.

In an embodiment, the dispersant may be combined with the dispersantdiluent at a suitable temperature, which may be at, below, or aboveambient temperature. In embodiments wherein the dispersant diluent maycomprise a viscous liquid, the dispersant may be combined with thedispersant diluent at substantially above ambient temperature, e.g., ata temperature in the range about 60° F. to 200° F., or from about 75° F.to 150° F.

In an embodiment, each of Composition A and Composition B may bephysically and chemically stable, and each of Composition A andComposition B can be transported, moved, and manipulated, for example,by pumping, either separately or following the combining of CompositionsA and B to form Composition C.

In another embodiment, Composition C may be prepared by separatelycombining one or more dispersant components with Composition A. As anexample, one or more materials selected from polyisobutylenesuccinimide, carboxylic acids, and dicarboxylic acids, may be addedseparately to Composition A.

In another embodiment, the method of preparing a hydroprocessingco-catalyst composition may further include combining Composition C witha catalyst introduction diluent to provide a Composition D, whereinComposition D may comprise a diluted suspension of the co-catalystparticles. In an embodiment, the catalyst introduction diluent may bemiscible with the liquid carrier and with the dispersant diluent. Thecatalyst introduction diluent may be further miscible with a hydrocarbonfeed having a boiling range up to at least about 650° F. The dispersantof the co-catalyst composition may promote dispersion of the co-catalystparticles in at least one material selected from the liquid carrier, thedispersant diluent, the catalyst introduction diluent, the hydrocarbonfeed, and combinations thereof.

In an embodiment, the catalyst introduction diluent may comprise ahydrocarbonaceous oil. The catalyst introduction diluent may comprise,for example, petroleum derived oil. The catalyst introduction diluentmay have a boiling range from about 350° F. to 1125° F., or from about450° F. to 1100° F., or from about 650° F. to 1000° F. In an embodiment,the catalyst introduction diluent may comprise, for example, a refinerystream or a feedstock for a refinery process. Exemplary catalystintroduction diluents may include, without limitation, vacuum gas oil,light gas oil, diesel, light cycle oil, medium cycle oil, decant oil,flush oil, cutter stocks, and combinations thereof.

In an embodiment, the catalyst introduction diluent may be present inComposition D in an amount between about 50 vol. % and 99 vol. %, orbetween about 67 vol. % and 98 vol. %, or between about 75 vol. % and 95vol. %. In one embodiment, Composition C may be combined with thecatalyst introduction diluent at a diluent/Composition C volume ratio inthe range from about 1:1 to 100:1, or from about 2:1 to 50:1, or fromabout 3:1 to 20:1.

Methods for Introducing a Co-Catalyst Composition into a HydroprocessingSystem

In another embodiment, we provide a method of introducing co-catalystparticles into a hydroprocessing system. The method may includeproviding a Composition A comprising the co-catalyst particles and aliquid carrier. In an embodiment, the co-catalyst particles may besuspended in the liquid carrier. The co-catalyst particles may be in themicron size range. In an embodiment, the co-catalyst particles may havea particle size in the range from about 1 micron (μm) to 100 microns, orfrom about 2 microns to 60 microns, or from about 2 microns to 30microns. In another embodiment, the co-catalyst particles may have amean particle size between about 2 microns and 100 microns, or betweenabout 4 microns and 40 microns, or between about 4 microns and 30microns.

In an embodiment, Composition A may comprise from about 5 wt. % to 50wt. % of the co-catalyst particles, in another embodiment from about 10wt. % to 40 wt. %, or in a further embodiment from about 15 wt. % to 30wt. %. In an embodiment, Composition A may comprise from about 50 wt. %to 95 wt. % of the liquid carrier, or from about 60 wt. % to 90 wt. %,or from about 70 wt. % to 85 wt. %.

In an embodiment, the liquid carrier may comprise oil. Such oil maycomprise, for example, petroleum derived oil. In an embodiment, oilcomprising the liquid carrier may have a boiling range from about 350°F. to 1125° F., or from about 550° F. to 1100° F., or from about 550° F.to 950° F. As a non-limiting example, the liquid carrier may comprise amaterial selected from vacuum gas oil, light vacuum gas oil, heavyvacuum gas oil, lube oil base stock, heavy diesel, and combinationsthereof.

In an embodiment, the liquid carrier may be miscible with a liquidhydrocarbonaceous oil, such as that comprising a catalyst introductiondiluent or a hydrocarbon feed to a hydroprocessing system. In anembodiment, the liquid carrier may be miscible with the liquidhydrocarbonaceous oil over a broad temperature range. For example, theliquid carrier may be miscible with the liquid hydrocarbonaceous oil ata temperature in the range from about 150° F. to 700° F., or from about350° F. to 650° F., under hydroprocessing conditions (high pressure).

In an embodiment, the catalyst introduction diluent may comprise ahydrocarbonaceous oil. The catalyst introduction diluent may comprise,for example, petroleum derived oil. The catalyst introduction diluentmay have a boiling range from about 350° F. to 1125° F., or from about450° F. to 1100° F., or from about 650° F. to 1000° F. In an embodiment,the catalyst introduction diluent may comprise, for example, a refinerystream or a feedstock for a refinery process. Exemplary catalystintroduction diluents may include, without limitation, vacuum gas oil,light gas oil, diesel, light cycle oil, medium cycle oil, decant oil,flush oil, cutter stocks, and combinations thereof.

The method of introducing co-catalyst particles into a hydroprocessingsystem may further include providing a Composition B comprising adispersant and a dispersant diluent. Composition B may comprise fromabout 10 wt. % to 95 wt. % of the dispersant, or from about 20 wt. % to80 wt. %, or from about 30 wt. % to 70 wt. %.

In an embodiment, the dispersant may comprise a plurality of components.In one embodiment, the dispersant may comprise a polyisobutylenesuccinimide. In an embodiment, the dispersant may further comprise amaterial selected from carboxylic acids, dicarboxylic acids, andcombinations thereof. In an embodiment, the dispersant may comprisepolyisobutylene succinimide and a carboxylic acid such as oleic acid. Ina sub-embodiment, Composition B may comprise from about 5 wt. % to 40wt. %, or from about 10 wt. % to 30 wt. %, of polyisobutylenesuccinimide; and Composition B may further comprise from about fromabout 5 wt. % to 70 wt. %, or from about 30 wt. % to 65 wt. %, of oleicacid.

In an embodiment, the dispersant diluent may comprise oil. Such oil maycomprise, for example, petroleum derived oil. In an embodiment, oilcomprising the dispersant diluent may have a boiling range from about350° F. to 1125° F., or from about 550° F. to 1100° F., or from about550° F. to 950° F. As a non-limiting example, the dispersant diluent maycomprise a material selected from vacuum gas oil, light vacuum gas oil,heavy vacuum gas oil, lube oil base stock, heavy diesel, andcombinations thereof.

In an embodiment, the method of introducing co-catalyst particles into ahydroprocessing system may still further include combining Composition Awith Composition B to form a Composition C, wherein Composition C maycomprise a suspension of the co-catalyst particles. In an embodiment,Composition C may be agitated to maintain the co-catalyst particles insuspension until Composition C is to be used, e.g., diluted forintroduction of the co-catalyst particles into the hydroprocessingsystem. In an embodiment, the combining step may comprise combiningComposition A with Composition B at a Composition A/Composition B volumeratio in the range from about 1:20 to 60:1, or from about 1:10 to 50:1,or from about 1:5 to 45:1.

In another embodiment, Composition C may be prepared by separatelycombining one or more dispersant components with Composition A. As anexample, one or more materials selected from polyisobutylenesuccinimide, carboxylic acids, and dicarboxylic acids, may be addedseparately to Composition A.

The method of introducing the co-catalyst particles into ahydroprocessing system may yet further include, after the formation ofComposition C, contacting the co-catalyst particles with a hydrocarbonfeed of the hydroprocessing system.

In another embodiment, prior to contacting the co-catalyst particleswith the hydrocarbon feed, the method may further comprise dilutingComposition C with the catalyst introduction diluent to provide aComposition D comprising a diluted suspension of the co-catalystparticles. In an embodiment, Composition D may be suitable forintroduction, e.g., via injection, into a hydrocarbon feed to ahydroprocessing system. In an embodiment, the contacting step maycomprise contacting Composition D with the hydrocarbon feed such thatthe co-catalyst particles are entrained with the hydrocarbon feed withinthe hydroprocessing system.

Composition D could join the hydrocarbon feed at various locationswithin the hydroprocessing unit. This could include injectingComposition D directly into the hydrocarbon feed line, ensuring thatprovisions were made to ensure that Composition D will undergosufficient mixing at the injection point to fully disperse into thehydrocarbon feed, utilizing slurry flow principles known in the art,including but not limited to proper line sizing, geometry andorientation, utilization of a quill, static mixer, or the like.

The catalyst introduction diluent may be in the liquid state whencombined with Composition C. In an embodiment, the catalyst introductiondiluent may be miscible with each of the liquid carrier, the dispersantdiluent, and the hydrocarbon feed to the hydroprocessing system, andcombinations thereof. The catalyst introduction diluent may comprise,for example, petroleum derived oil. The catalyst introduction diluentmay have a boiling range from about 350° F. to 1125° F., or from about450° F. to 1100° F., or from about 650° F. to 1000° F. In an embodiment,the catalyst introduction diluent may comprise, for example, a refinerystream or a feedstock for a refinery process. Exemplary catalystintroduction diluents may include, without limitation, vacuum gas oil,light gas oil, diesel, light cycle oil, medium cycle oil, decant oil,flush oil, cutter stocks, and combinations thereof.

In an embodiment, the catalyst introduction diluent may be present inComposition D in an amount between about 50 vol. % and 99 vol. %, orbetween about 67 vol. % and 98 vol. %, or between about 75 vol. % and 95vol. %. For example, in one embodiment, Composition C may be combinedwith the catalyst introduction diluent at a diluent/Composition C volumeratio in the range from about 1:1 to 100:1, or from about 2:1 to 50:1,or from about 3:1 to 20:1.

During the step of diluting Composition C with the catalyst introductiondiluent, the catalyst introduction diluent may be at a temperature inthe range from about ambient temperature to 700° F., or from about 350°F. to 650° F., or from about 450° F. to 600° F. In an embodiment,Composition C may be maintained at about ambient temperature, prior tocombining the co-catalyst composition with the catalyst introductiondiluent. In another embodiment, Composition C may be pre-heated prior tocombining the co-catalyst composition with the catalyst introductiondiluent. During the contacting step, the hydrocarbon feed may be at atemperature in the range from about 350° F. to 750° F., or from about350° F. to 650° F., or from about 450° F. to 600° F. In an embodiment,the hydrocarbon feed may comprise heavy oil, such as vacuum residuum oratmospheric residuum, having a boiling range up to at least about 650°F.

The dispersant may promote dispersion of the co-catalyst particles in atleast one of the liquid carrier, the dispersant diluent, the catalystintroduction diluent, the hydrocarbon feed, or combinations thereof. Inan embodiment, the dispersant may comprise polyisobutylene succinimide.In an embodiment, the dispersant may further comprise a materialselected from carboxylic acids, dicarboxylic acids, and combinationsthereof. In an embodiment, the dispersant may comprise polyisobutylenesuccinimide and oleic acid. In an embodiment, Composition C may comprisefrom about 0.5 wt. % to 10.0 wt. % of polyisobutylene succinimide, orfrom about 1.0 wt. % to 7.5 wt. %, or from about 1.5 wt. % to 5.0 wt. %of polyisobutylene succinimide. In an embodiment, Composition C mayfurther comprise from about 1.0 wt. % to 15.0 wt. % of oleic acid, orfrom about 2.0 wt. % to 10.0 wt. %, or from about 3.0 wt. % to 7.5 wt. %of oleic acid.

In another embodiment, a method of introducing co-catalyst particlesinto a hydroprocessing system may include providing a Composition Acomprising the co-catalyst particles and a liquid carrier. Composition Amay comprise from about 5 wt. % to 50 wt. % of the co-catalyst particlesand from about 50 wt. % to 95 wt. % of the liquid carrier. In anembodiment, the liquid carrier may comprise oil. Such oil may comprise,for example, petroleum derived oil. In an embodiment, oil comprising theliquid carrier may have a boiling range from about 350° F. to 1125° F.,or from about 550° F. to 1100° F., or from about 550° F. to 950° F. As anon-limiting example, the liquid carrier may comprise a materialselected from vacuum gas oil, light vacuum gas oil, heavy vacuum gasoil, lube oil base stock, heavy diesel, and combinations thereof.

In an embodiment, the co-catalyst particles may have a particle size inthe range from about 1 micron (μm) to 100 microns, or from about 2microns to 60 microns, or from about 2 microns to 30 microns. In anotherembodiment, the co-catalyst particles may have a mean particle sizebetween about 2 microns and 100 microns, or between about 4 microns and40 microns, or between about 4 microns and 30 microns.

The co-catalyst particles may comprise a support. The support maycomprise a material selected from alumina, aluminosilicates, silica, aswell as other refractory inorganic oxides, including boria, magnesia,titania, and the like, and combinations thereof. The co-catalyst supportof the present invention can be manufactured by any conventionaltechniques. In an embodiment, the co-catalyst particles may furthercomprise one or more metal components. In an embodiment, the support orbase may contain catalytic metals, in particular metals from Group VIBof the Periodic Table, including molybdenum and/or tungsten, and/or fromGroup III of the periodic Table, in particular nickel and/or cobalt.Catalytic metals may be placed onto the support by conventionaltechniques, including comulling, impregnation, and the like.

The method of introducing co-catalyst particles into a hydroprocessingsystem may further include providing a Composition B comprising adispersant and a dispersant diluent. In an embodiment, the dispersantmay comprise polyisobutylene succinimide. In an embodiment, thedispersant may further comprise a material selected from carboxylicacids, dicarboxylic acids, and combinations thereof.

In an embodiment, the dispersant diluent may comprise oil. In anembodiment, oil comprising the dispersant diluent may have a boilingrange from about 350° F. to 1125° F., or from about 550° F. to 1100° F.,or from about 550° F. to 950° F. As a non-limiting example, thedispersant diluent may comprise a material selected from vacuum gas oil,light vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavydiesel, and combinations thereof.

The method of introducing co-catalyst particles into a hydroprocessingsystem may further include combining Composition A with Composition B toform a Composition C, and combining Composition C with a catalystintroduction diluent to provide a composition D. The catalystintroduction diluent may be miscible with Composition C. In anembodiment, the catalyst introduction diluent may comprise oil.

The method of introducing co-catalyst particles into a hydroprocessingsystem may still further include contacting composition D with thehydrocarbon feed of the hydroprocessing system. Composition D may bemiscible with the hydrocarbon feed. In an embodiment, Composition D maybe combined with the hydrocarbon feed such that the co-catalystparticles are entrained with the hydrocarbon feed within thehydroprocessing system.

In yet another embodiment, a method of introducing co-catalyst particlesinto a hydroprocessing system may include providing a Composition Acomprising the co-catalyst particles and a liquid carrier. Theco-catalyst particles may comprise a support comprising a materialselected from alumina, aluminosilicates, silica, boria, magnesia,titania, and combinations thereof, and the co-catalyst particles mayhave a mean particle size between about 2 microns and 100 microns.

The method of introducing co-catalyst particles into a hydroprocessingsystem may further include providing a Composition B comprising adispersant and a dispersant diluent. In an embodiment, the dispersantmay comprise polyisobutylene succinimide. In an embodiment, thedispersant may further comprise a material selected from carboxylicacids, dicarboxylic acids, and combinations thereof. In one embodiment,the dispersant may comprise polyisobutylene succinimide and a carboxylicacid such as oleic acid.

In an embodiment, the dispersant diluent may comprise oil. In anembodiment, oil comprising the dispersant diluent may have a boilingrange from about 350° F. to 1125° F., or from about 550° F. to 1100° F.,or from about 550° F. to 950° F. As a non-limiting example, thedispersant diluent may comprise a material selected from vacuum gas oil,light vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavydiesel, and combinations thereof.

The method of introducing co-catalyst particles into a hydroprocessingsystem may still further include combining Composition A withComposition B to form a Composition C, wherein Composition C comprises asuspension of the co-catalyst particles. The method may yet furtherinclude diluting Composition C with a catalyst introduction diluent toprovide a composition D comprising a diluted suspension of theco-catalyst particles, or direct injection of Composition C into thehydroprocessing unit. The catalyst introduction diluent may compriseoil, and the catalyst introduction diluent may be miscible withComposition C.

After the diluting step, Composition D may be contacted with ahydrocarbon feed of the hydroprocessing system, wherein Composition Dmay be miscible with the hydrocarbon feed. The hydrocarbon feed may havea boiling range >650° F. and/or >950° F. In an embodiment, thecontacting step may comprise contacting the co-catalyst particles withthe hydrocarbon feed such that the co-catalyst particles are entrainedwith the hydrocarbon feed within the hydroprocessing system.

According to methods and compositions disclosed herein, co-catalystparticles introduced into a hydroprocessing system may be present in thehydrocarbon feed at a concentration up to about 600 ppm, or from about20 ppm to 500 ppm, or from about 100 to 400 ppm. In an embodiment, theco-catalyst particles may be entrained with the hydrocarbon feed so asto freely migrate with the hydrocarbon feed through at least a portionof the hydroprocessing system, and in another embodiment the co-catalystparticles may be entrained with the hydrocarbon feed so as to freelymigrate with the hydrocarbon feed throughout the entire hydroprocessingsystem.

The hydrocarbon feed may be in the liquid state when contacted with theco-catalyst particles. In an embodiment, when the hydrocarbon feed iscontacted with the co-catalyst particles during the contacting step, thehydrocarbon feed may be at a temperature in the range from about 350° F.to 750° F., or from about 350° F. to 650° F., or from about 450° F. to600° F. In an embodiment, and as a non-limiting example, the hydrocarbonfeed may comprise heavy oil having a boiling range up to at least about650° F.

In one embodiment, fresh co-catalyst, e.g., in the form of a CompositionC/catalyst introduction diluent mixture, may be added to thehydroprocessing system as a single addition; or in another embodiment,the fresh co-catalyst may be added to the hydroprocessing systemintermittently; while in a further embodiment, the fresh co-catalyst maybe added to the hydroprocessing system continuously.

In other embodiments fresh co-catalyst, e.g., in the form of aComposition C only, may be added directly to the hydroprocessing systemin the absence of a catalyst introduction diluent, either as a singleaddition, intermittently, or continuously.

During hydroprocessing, the dispersant may eventually decompose to yieldonly species that are entirely compatible with the hydroprocessingprocess and that will not interfere with the products ofhydroprocessing. In an embodiment, at least substantially all of thedispersant may be converted or decomposed, under hydroprocessingconditions in the hydroprocessing system, to yield light hydrocarbons,for example, predominantly C₁-C₄ hydrocarbons.

EXAMPLES

The following illustrative examples are intended to be non-limiting.

Example 1 Preparation of a Suspension of Co-Catalyst Particles UsingVacuum Gas Oil as Liquid Carrier

43 g of co-catalyst particles were combined with 100 g of vacuum gas oil(VGO) (see Table 1). The mixture was agitated for 5 minutes using aspatula to provide a co-catalyst composition in the form of a slurrycomprising a suspension of the co-catalyst particles in the VGO. Theco-catalyst solids content of the co-catalyst composition of Example 1was about 30 wt. %.

Example 2 Preparation of a Suspension of Co-Catalyst Particles UsingVacuum Gas Oil as Liquid Carrier and Dispersants

43 g of co-catalyst particles (per Example 1) were combined with 100 gof VGO (see Table 1), 2.2 g of polyisobutylene succinimide, and 5.4 g ofoleic acid. The mixture was agitated for 5 minutes using a spatula toprovide a co-catalyst composition in the form of a slurry comprising asuspension of the co-catalyst particles in the VGO and dispersants. Theco-catalyst solids content of the co-catalyst composition of Example 2was about 28.6 wt. %. The addition of dispersants in Example 2 led toimproved solids dispersion (see Table 2), as measured using aMettler-Toledo Focused Beam Reflectance Measurement (FBRM) probe,relative to Example 1.

Example 3 Preparation of a Co-Catalyst Containing Material Using MediumCycle Oil and Dispersants

43 g of co-catalyst particles (per Example 1) were combined with 100 gof medium cycle oil (MCO) (see Table 1), 2.2 g of polyisobutylenesuccinimide, and 5.4 g of oleic acid. The mixture was agitated as forExample 1. The use of MCO in the protocol of Example 3, led to poorco-catalyst solids dispersion (see Table 2), even in the presence ofdispersants.

TABLE 1 Feed Description MCO VGO Feed ID ABQ0888 ABQ0297 Feed API 10.720.9 Feed Sulfur, wt % 0.3980 2.2130 Feed Nitrogen, ppm 640 1247Distillation wt % ° F. ° F. 0.5 403 567 5 480 694 10 490 741 15 499 77020 517 788 25 524 802 30 532 814 40 546 832 50 568 849 60 583 865 70 606882 75 620 892 80 630 903 85 651 917 90 669 934 95 699 961 99 762 1003  99.5 787 1014 650° F.− 84.8 2.1 650-950° F.    15.2 91.2 950° F.+ 0.06.7

TABLE 2 Example 1 Example 2 Example 3 Co-Catalyst Solids, g 43 43 43 OilCarrier Type VGO VGO MCO Oil Carrier, g 100 100 100 Dispersantpolylsobutylene 0 2.2 2.2 succinimide, g Dispersant Oleic Acid, g 0 5.45.4 Solids Concentration, wt. % 30.1 28.6 28.6 ParticieSize Distribution0-10 μm (% Count) 91.9 96.0 80.7 10-20 μm (% Count) 6.2 3.5 9.0 >20 μm(% Count) 1.9 0.5 10.3

Where permitted, all publications, patents and patent applications citedin this application are herein incorporated by reference in theirentirety, to the extent such disclosure is not inconsistent withembodiments of the present invention.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used herein are to be understoodas being modified in all instances by the term “about.” It is notedthat, as used in this specification and the appended claims, thesingular forms “a,” “an,” and “the,” include plural references unlessexpressly and unequivocally limited to one referent.

Unless otherwise specified, the recitation of a genus of elements,materials or other components, from which an individual component ormixture of components can be selected, is intended to include allpossible sub-generic combinations of the listed components and mixturesthereof. Also, “include” and its variants are intended to benon-limiting, such that recitation of items in a list is not to theexclusion of other like items that may also be useful in the materials,compositions and methods disclosed herein.

Numerous variations of the disclosed compositions and methods may bepossible in light of the teachings herein. It is therefore understoodthat within the scope of the following claims, embodiments of theinvention may be practiced otherwise than as specifically described orexemplified herein.

What is claimed is:
 1. A method of introducing co-catalyst particlesinto a hydroprocessing system, the method comprising: a) providing acomposition A comprising the co-catalyst particles and a liquid carrier;b) providing a composition B comprising a dispersant and a dispersantdiluent; c) combining composition B with composition A to form acomposition C, wherein composition C comprises a suspension of theco-catalyst particles; and d) after step c), contacting the co-catalystparticles with a hydrocarbon feed of the hydroprocessing system.
 2. Themethod of claim 1, wherein step d) comprises contacting the co-catalystparticles with the hydrocarbon feed such that the co-catalyst particlesare entrained with the hydrocarbon feed within the hydroprocessingsystem.
 3. The method of claim 1, wherein the dispersant comprisespolyisobutylene succinimide.
 4. The method of claim 3, wherein thedispersant further comprises a material selected from the groupconsisting of carboxylic acids, dicarboxylic acids, and combinationsthereof.
 5. The method of claim 3, wherein the dispersant furthercomprises oleic acid.
 6. The method of claim 1, wherein: the co-catalystparticles have a mean particle size between about 2 microns and 100microns, and the co-catalyst particles comprise a support comprising amaterial selected from the group consisting of alumina,aluminosilicates, silica, boria, magnesia, titania, and combinationsthereof.
 7. The method of claim 1, wherein the co-catalyst particleshave a mean particle size between about 4 microns and 40 microns.
 8. Themethod of claim 1, wherein composition A comprises from about 5 wt. % to50 wt. % of the co-catalyst particles and from about 50 wt. % to 95 wt.% of the liquid carrier.
 9. The method of claim 1, wherein the liquidcarrier comprises oil.
 10. The method of claim 9, wherein: theco-catalyst particles are hydrophilic, and step a) comprises suspendingthe co-catalyst particles in the liquid carrier.
 11. The method of claim1, wherein the liquid carrier comprises a material selected from thegroup consisting of vacuum gas oil, light vacuum gas oil, heavy vacuumgas oil, lube oil base stock, heavy diesel, and combinations thereof.12. The method of claim 1, wherein the hydrocarbon feed comprises heavyoil feedstock having a boiling range up to at least about 650° F. 13.The method of claim 1, wherein during step d) the hydrocarbon feed is ata temperature in the range from about 350° F. to 750° F.
 14. The methodof claim 1, further comprising: e) prior to step d), dilutingcomposition C with a catalyst introduction diluent to provide a dilutedsuspension of the co-catalyst particles.
 15. The method of claim 14,wherein: the catalyst introduction diluent comprises oil having aboiling range from about 350° F. to 1125° F., and during step e) thecatalyst introduction diluent is at a temperature in the range fromabout ambient temperature to 700° F.
 16. A method of introducingco-catalyst particles into a hydroprocessing system, the methodcomprising: a) providing a composition A comprising the co-catalystparticles and a liquid carrier, wherein the co-catalyst particles have amean particle size between about 2 microns and 100 microns, and theliquid carrier comprises oil; b) providing a composition B comprising adispersant and a dispersant diluent; c) combining composition A withcomposition B to form a composition C; and d) contacting composition Cwith a hydrocarbon feed of the hydroprocessing system.
 17. The method ofclaim 16, wherein: the hydrocarbon feed comprises heavy oil feedstockhaving a boiling range up to at least about 650° F., and during step d)the hydrocarbon feed is at a temperature in the range from about 350° F.to 750° F.
 18. The method of claim 16, wherein step d) comprisescontacting composition C with the hydrocarbon feed such that theco-catalyst particles are entrained with the hydrocarbon feed within thehydroprocessing system.
 19. A method of introducing co-catalystparticles into a hydroprocessing system, the method comprising: a)providing a composition A comprising the co-catalyst particles and aliquid carrier, wherein the co-catalyst particles comprise a supportcomprising a material selected from the group consisting of alumina,aluminosilicates, silica, boria, magnesia, titania, and combinationsthereof, and the co-catalyst particles have a mean particle size betweenabout 2 microns and 100 microns; b) providing a composition B comprisinga dispersant and a dispersant diluent; c) combining composition B withcomposition A to form a composition C, wherein composition C comprises asuspension of the co-catalyst particles; and d) contacting composition Cwith a hydrocarbon feed of the hydroprocessing system such that theco-catalyst particles are entrained with the hydrocarbon feed within thehydroprocessing system.
 20. The method of claim 19, wherein compositionC is miscible with the hydrocarbon feed, and the hydrocarbon feedcomprises heavy oil feedstock having a boiling range up to at leastabout 650° F.